Process of halogenizing perylene



i v hydrobromic ac1 Patented 1926;-

I ALOIS ZINKE A ND ALFRED PONGRATZ, OF GRATZ, AUSTRIA, ASSIGI IORS BEUSA,-F GENOA, ITALY.

1,580,708 ATE OFFICE.

To ration rnocEs's or moemrzirm imam No Drawing.

To all whom it may concern: 7 Be it known that A oIs ZINKE and ALFRED PoNcRATz, both citizens of the Republic of Austria, residing at Gratz, Styria, Republic I of Austria, have invented certain new and useful Improvements in Processes of Halogenizing Perylene, of which the following is a specification. V

. It has already been proposed to roduce I0 halogen derivatives of perylene by direct action ofhalogens on-perylene, but in this way it was impossible to obtain with certainty products of .apredetermined composition. The products obtained according to the pres- 1 ent invention by the action of halogens in status 'nascendi on perylene are essentially difierent from those heretofore known. Moreover, the improved process ofiers the advantage that the quantity of nascent halo gen used may be easily controlled and therey different substituted halogen perylenes may be obtained. v v

The following is a description of examples of carrying into practice the improved .2 process.

Ewwmple I.

1 part by weight of perylene is suspended in 20 parts by weight of glacial acetlc acid and; 2 parts by weight of sodiumlbromite are added thereto. Then 1.2 parts by weight I of peroxide of hydrogen diluted with glacial acetic acid to 12 parts by weight are added drop by-drop in t e course of one hour under continuous agitation. .At the end of the reaction the product of the latter is deposited in the form of reddish brown flakes,

whereu on the product is purified after sucking 01f y recrystallization from nitrobenzol. 40 The pure productv forms yellowish brown laminae oi-"scales having a bright lustre and a melting point of 222 to 224 centigrade, and is a dibromide. derivative. In concentrated sulphuric acid it dissolves with a red-- dish violet colour. It is insoluble in the cold in water and the usual solvents having a.

comparativelylowi boiling temperature, in the usual solvents having a comparatively highboiling temperature it is little soluble in the cold. In the heat it is soluble in xylol, aniline and nitrobenzol. I

' By brominating perylene b the action of on peroxi e of hydrogen III a suspension in glacial acetic acid an oxidized brominated product is. obtained in the Application: filedApril '2,- ma. Serialin. areas.

form of a yellow powder which is partly soluble in caustic lyes. By the addition of sodlum hydrosulphite-a reddish violet vat is obtained in which cotton is dyed in beautiful brown colours. I Y

Furthermore pure perylene chlorides are obtained by causing nascent chlorine to act on perylene in such a manner that the chlorine is obtained by the oxidation of hydro- V chloric acid With-peroxide of hydrogen, and 5 the chlorination is carried out'in a suspension of finely powdered .pery-lene in solvents, such as glacial acetic acid. By var g the quantity of chlorine, various suli s ituted perylene chlorides may be obtained 7 7 Example II.' a 1 part by weight of perylene is suspended in 20 parts by weight of glacial acetic acid and 4 parts by weight of 40% hydrochloric acid are added. Then the suspension is brought .to a temperature of about 80 centi grade and a solution of 1.8 parts by Weight of 30% peroxide of hydrogen is caused to gradually flow into the suspension in the 80 course of four hours under agitation. After settling theliquid is decanted and the remainder thereof is separated from the deposit by filtering whereupon the depositv is washed with glacial acetic acid and subsequently with water and is dried.

The compound crystallizes from anilin, nitrobenzol, glacial acetic acidand toluol' in yellow needles having a melting temperature of 242 centigrade, in concentrated sulphuric acid it is soluble with a= reddish violetcolour and, according with the results of analysis it is a tetra'chlorid of perylene. If

.in tl1e reaction above described .the quantity is obtained which according to analysis a pears to be a. dichlorid of perylene, but whidli probably is a Y By the action of nascent chlorine obtamed oxide and the like in the suspension or solution mainly oxidized, chlorinated 'products which dye cotton yellow to brown from a red vat are formed.

What is claimed is:

A process foimanufacturing halogen derivatives of perylene, consisting in suspendmg perylene in a state of fine subdivision in a hquid and introducing into the same simultaneously and gradually a substance capable V ofrevolving halogen, and an oxidizing agent capable of liberating halogen therefrom; both the said substances and the oxidizing agent 1 being indifferent to perylene and the liquid in which it is suspended.

' In testimony whereof we have afii xed our signatures.

ALOIS ZINKE. ALFRED PONGRATZ; 

